The invention relates to dioxazine compounds containing sulphonic acid groups and salts thereof and mixtures of these compounds which may be in internal or external salt form. They are suitable for use as dyestuffs.
According to the invention there are provided compounds of formula (I) 
wherein
R1 signifies xe2x80x94NH2 or 
xe2x80x83wherein
R5 signifies hydrogen or C1-4-alkyl,
X and Y independently signify halogen or hydroxy or C1-3-alkoxy or phenoxy or the radical of a cyclic, an aliphatic, an araliphatic or an aromatic amine linked over the amine-nitrogen and optionally substituted by hydroxy, carboxy, alkoxy, alkyl and/or sulphonic acid groups or the rest of a heterocyclic amine linked over the amine-nitrogen,
Z signifies halogen or the radical of a cyclic, an aliphatic or an araliphatic amine linked over the amine-nitrogen and optionally substituted by hydroxy, carboxy, alkoxy and/or sulphonic acid groups or the rest of a heterocyclic amine linked over the amine-nitrogen,
R2 signifies xe2x80x94NH2 or 
xe2x80x83with the same definitions for R5, X and Y as above or
R2 is the moiety (b) 
xe2x80x83wherein
P signifies xe2x80x94SO3H, xe2x80x94COOH or xe2x80x94OH,
Q signifies a xe2x80x94NHxe2x80x94 radical or a group selected from 
xe2x80x83wherein the asterisk marks the bond attached to the phenyl ring,
Z signifies the same as above,
n has the value 0, 1, 2,
R3 signifies xe2x80x94NR6 
in which R6 signifies hydrogen or a C1-4-alkyl radical or
R3 is the rest (a) 
xe2x80x83wherein all substituents have the same meanings as defined above,
R4 signifies hydrogen or C1-4-alkyl,
T1 and T2 independently from each other signify hydrogen, halogen, C1-6-alkyl or C1-4-alkoxy,
M signifies hydrogen or a cation;
salts thereof and mixtures of such compounds and/or salts.
Preferred compounds of formula (I), wherein all substituents have same meanings as defined above, have the provisos that
(i) when R1 and R2 is xe2x80x94NH2 then R3 is 
xe2x80x83wherein P, Q, Z and n have the same meanings as defined above,
(ii) when R1 is xe2x80x94NH2 and R2 is 
xe2x80x83wherein P, Q, Z and n have the same meaning as defined above, then R3 is xe2x80x94NHxe2x80x94;
salts thereof and mixtures of such compounds and/or salts.
In further preferred compounds of formula (I) both R1 and R2 signify 
wherein
R5 signifies hydrogen or C1-4-alkyl, and
R3 signifies xe2x80x94NR6 
in which R6 signifies hydrogen or a C1-4-alkyl radical and all the other substituents have the definition as defined above,
salts thereof and mixtures of such compounds and/or salts.
In further preferred compounds the radicals X, Y and Z contain no chromophoric group.
In other preferred,compounds any amine Hxe2x80x94X, Hxe2x80x94Y or Hxe2x80x94Z has a molecular weight in the range of 50 to 500, preferably 50 to 400. Where such an amine contains ring systems, it preferably contains 1 to 4 rings and most preferably has only 1 or 2 rings. Such amine preferably contains at least one hydrophilic group which independently can be anionic, cationic or non-ionogenic. Examples of anionic hydrophilic groups are carboxy or sulphonic acid groups. Examples of cationic hydrophilic groups are mono-(C1-4-alkyl)- or di(C1-4-alkyl)amino groups comprising a protonatable nitrogen atom or a quaternary ammonium group, wherein each C1-4-alkyl group can be substituted by halogen, hydroxy, C1-4-alkoxy, phenyl or phenoxy. Any phenyl or naphthyl ring present in the amine may be unsubstituted or substituted by one, two or three groups selected from halogen, hydroxy, C1-4-alkyl, C1-4-alkoxy, phenoxy, carboxy or sulphonic acid. Any heterocyclic ring present in the amine is a 5- or 6-membered ring containing one or two hetero atoms selected from N, O or S, which heterocyclicring is unsubstituted or substituted by one or two C1-4-alkyl groups.
Preferred Hxe2x80x94Z are ammonia and aliphatic amines, preferably substituted with a hydroxy, carboxy, alkoxy or sulphonic acid group, e.g. ethanolamine, diethanolamine, isopropanolamine, diisopropanolamine, 2-amino-hydroxypropane, glycine, N-methyl-ethanolamine, 3-methoxy-propylamine, l-aminoethyl-2-sulfonic acid and most preferably, 1-methylamino-ethyl-2-sulfonic acid; heterocyclic amines, e.g. morpholine, piperazine or hydroxy-ethylpiperazine; or N,N-diethylaminopropylamine and 1,2-diaminopropane.
Most preferred Hxe2x80x94Z is 1-methylamino-ethyl-2-sulfonic acid.
In a further preferred compound or mixture M is hydrogen or a colorless cation or M is a cationic portion in a substituent X, Y or Z containing a cationic charge, to form an inner salt.
In a further aspect of the present invention there are provided mixtures containing
a) a compound of formula (Ia) C
xe2x80x83wherein R3xe2x80x2 is a divalent radical of formula (a), R2xe2x80x2 is xe2x80x94NH2 and Z has the same meaning as defined above;
b) a compound of the above formula (Ia) wherein R3xe2x80x2 is xe2x80x94NHxe2x80x94, R2xe2x80x2 is a radical of formula (b) and Z has the same meaning as defined above;
c) a compound of formula (II) 
xe2x80x83wherein Q, P and n have the same meaning as defined above and Zxe2x80x2 has the same definition as Z, additionally Zxe2x80x2 can be an aromatic amine, preferably for the component c) Zxe2x80x2 is a radical of formula (c) 
d) a compound of formula (II), wherein Z has the same meanings as defined above, except halogen, preferably for the component d) Zxe2x80x2 is a radical of formula (d) 
e) a compound of formula (III) 
xe2x80x83wherein Zxe2x80x2 has the definition as defined above,
or salts of such compounds.
The present invention further provides a process for the preparation of a compound of formula (Ib) 
according to formula (I) with the same definitions of the substituents as defined above,
wherein one mole of a compound of formula (IV) 
or a mixture of compounds of formula (IV) with the same definitions of the substituents as in formula (Ib) is reacted with two moles of at least one compound of formula (V) 
wherein Hal signifies halogen, preferably chlorine, and X and Y independently have the same meanings as defined above, under dehydrohalogenating conditions, and, if in formula (Ib) anyone of X and Y has a significance other than halogen while in formula (V) the corresponding X or Y signifies halogen, and/or if in formula (Ib) Z has a significance other than halogen, the obtained condensation product of formula (VI) 
with the same definitions of the substituents as in formula (Ib) is reacted, with at least one corresponding amine of formula Hxe2x80x94X Hxe2x80x94Y and/or Hxe2x80x94Z, which have the same definitions as above and/or an alkali metal C1-3-alcoholate or phenolate, as required. The oxidation of the leuco form to the dioxazine form takes place after the condensation step(s) or simultaneously with the exchange of halogen for amine.
The compounds of formula (Ib) thus obtained may be isolated in accordance with known methods.
The compounds of formula (Ib) containing free basic groups may be converted wholly or in part into water-soluble salts by reacting with any inorganic or organic acids. The compounds of formula (Ib) containing carboxy or sulphonic acid groups may also be converted into water-soluble salts by reacting with any basic compound.
The starting compounds, the amines of formula (IV) in the leuco form may be prepared by step-wise replacement of the chlorine atoms of cyanuric chloride whereby in a first and second step cyanuric chloride is reacted with a dioxazine compound of formula (VII) 
which can be identical or different, depending on the meanings of R5.
Before the reaction with a compound of the formula (V), the intermediately obtained dyestuff is brought into the leuco form of formula (IV) by reduction. This reduction process can be performed catalytically with hydrogen (and the usual catalysts palladium, platinum or nickel) or with other metals like iron, tin or zinc in the presence of acids. Alternatively, the reduction can be performed with sodium dithionite in water at pH values from 6 to 9, preferably 6.5 to 7.5, and temperatures from 15 to 45xc2x0 C., preferably 20 to 30xc2x0 C. The reducing agent is suitably used in double or triple molar amounts of the dyestuff to be reduced and all reduction and condensation reactions are performed in inert atmosphere, e.g. under nitrogen.
The compounds of formula (V) may also be prepared by step-wise replacement of the chlorine atoms of cyanuric chloride whereby in a first and/or second step, cyanuric chloride is reacted with an amine of formula HX and/or an amine of formula HY.
In the case where identical amino groups have to be introduced, this first and second steps may be combined into one step. Suitably, the single step is carried out at temperatures from 0-30xc2x0 C. and preferably at pH 4-6.
Where different amino groups have to be introduced, suitably, the amine showing the higher selectivity with respect to the condensation reaction is introduced in the first step at a temperature of preferably 0-20xc2x0 C. more preferably 0-5xc2x0 C. Both condensation steps may be carried out using the conventional reaction medium where the upper limit of pH is 7. The second step is preferably carried out at 10-40xc2x0 C., more preferably 12-30xc2x0 C.
The starting compounds of formulae (VI), HX and HY are either known or may be prepared in accordance with known methods from available starting materials.
The present invention further provides a process for the preparation of compounds of the formula (Ia), 
according to formula I wherein either
R3xe2x80x2 is a divalent radical of formula (a) 
xe2x80x83wherein P, Q, Z and n have the same meanings as defined above and R2xe2x80x2 is xe2x80x94NH2; or
R3xe2x80x2 is xe2x80x94NHxe2x80x94 and
R2xe2x80x2 is a radical of formula (b) 
xe2x80x83wherein P, Q, Z and n have the same meanings as defined above,
salts thereof and of mixtures of such compounds and/or salts, which comprises reacting a compound of formula (VIII) 
xe2x80x83wherein either R3xe2x80x3 is a divalent radical of formula (axe2x80x2) 
xe2x80x83wherein P, Q and n have the same meanings as defined above
and R2xe2x80x3 is xe2x80x94NH2; or R3xe2x80x3 is xe2x80x94NHxe2x80x94 and R2xe2x80x3 is a radical of formula (bxe2x80x2) 
xe2x80x83wherein P, Q and n have the same meanings as defined above or a mixture of such compounds with an amine Hxe2x80x94Z or Hxe2x80x94Zxe2x80x2 and, if desired, converting compounds of formula (I) thus obtained into salts or salts thus obtained into compounds of formula (I) or into other salts.
The compounds of the above formula (VIII) can be prepared by reacting a compound of formula (IX) 
with about one equivalent of 2,4,6-trichlorotriazine, reacting the product of formula (X) 
thus obtained with 1,4-diaminobenzene-2-sulfonic acid and reacting the product (XI) 
thus obtained with another portion of the compound of the above formula (X).
The compound of the above formula (X) can react (rather than with the 1,4-diaminobenzene-2-sulfonic acid) with any unreacted compound of the above formula (IX) and thus give a compound corresponding to the above formula (III) but in which Zxe2x80x2 is chloro which, in the ultimate treatment with an amine Hxe2x80x94Zxe2x80x2, gives a compound of the above formula (III) in which Zxe2x80x2 is a radical as defined above. Similarly, the compound (XI) obtained when reacting a compound of the above formula (X) with 1,4-diaminobenzene-2-sulfonic acid can react (rather than with another portion of the compound of formula (X)) with any unreacted 1,4-diaminobenzene-2-sulfonic acid to give a compound of the above formula (II) wherein Z a radical of the above formula (c), or in the ultimate treatment with an amine Hxe2x80x94Z give a compound of the above formula (II) wherein Z is a radical of formula (d) or a radical as defined above. Thus, when
a) reacting a compound of the above formula (IX) with about one equivalent of 2,4,6-trichlorotriazine;
b) reacting the compound of the above formula (X) thus obtained with 1,4-diaminobenzene-2-sulfonic acid;
c) reacting the compound of the above formula (XI) thus obtained with another portion of the compound of the above formula (X); and
d) reacting the product thus obtained with an amine;
there is obtained a mixture as defined hereinabove comprising
a) a compound of the above formula (Ia) wherein R3xe2x80x2 is a divalent radical of the above formula (a) and R2xe2x80x2 is xe2x80x94NH2 and Z as defined above;
b) a compound of the above formula (Ia) wherein R3xe2x80x2 is xe2x80x94NHxe2x80x94 and R2xe2x80x2 is a radical of the above formula (b) and Z as defined above;
c) a compound of the above formula (II) wherein Zxe2x80x2 is a radical of the above formula (c) and all the other substituents have the same meanings as defined above;
d) a compound of the above formula (II) wherein Zxe2x80x2 is a radical of an amine, preferably a radical of formula (d) and all the other substituents have the same meanings as defined above and
e) a compound of the above formula (III) wherein Zxe2x80x2 is a radical of an amine,
or salts of these compounds.
If desired, a mixture of compounds thus obtained can be converted into a mixture of corresponding salts and, similarly, a mixture of salts thus obtained can be converted into a mixture of the corresponding compounds or into a mixture of other salts.
It will be appreciated that the relative quantities of the components of the mixture will depend on, inter alia, the exact reaction conditions used when preparing this mixture. In general, however, these relative quantities are approximately as follows:
Component a): 30-40%;
Component b): 30-47%;
Component c): 1.5-8%;
Component d): 2-11%; and
Component e): 12.5-23.5%.
Suitable amines Hxe2x80x94Zxe2x80x2 are ammonia and aliphatic amines, preferably substituted with a hydroxy, carboxy, alkoxy and/or sulphonic acid group, e.g. ethanolamine, diethanolamine, isopropanolamine, diisopropanolamine, 2-amino-hydroxypropane, glycine, N-methyl-ethanolamine, 3-methoxy-propylamine, 1-aminoethyl-2-sulfonic acid and most preferably, 1-methylamino-ethyl-2-sulfonic acid; aromatic amines, preferably substituted with a carboxy or sulphonic acid group, e.g. aniline, 4- or 3-sulpho-aniline, 4- or 3-carboxy-aniline; and heterocyclic amines, e.g. morpholine, piperazine or hydroxyethylpiperazine; or N,N-diethylaminopropylamine and 1,2-diaminopropane.
Suitable amines Hxe2x80x94Z are the same as for Hxe2x80x94Zxe2x80x2 except the aromatic amines, with the proviso, that very reactive aromatic amines are suitable.
The compound of formula (IX), 3,10-diamino-6,13-dichloro-4,11-triphendioxazine disulphonic acid, is known. For the reaction with the 2,4,6-trichlorotriazine, the compound of formula (IX) is conveniently taken up in water, and the pH is brought to about 8.0-8.5 by addition of caustic alkali, preferably an aqueous lithium hydroxide solution. The 2,4,6-trichlorotriazine is conveniently utilized in the form of an aqueous suspension containing a small amount of a conventional surfactant, which is slowly added, under cooling to a temperature of about 0-10xc2x0 C., preferably about 5-8xc2x0 C., to the aqueous solution of the compound of formula (IX) under stirring, the pH of the reaction mixture being kept at about 8.0-8.5 by continuous addition of further caustic alkali, preferably aqueous lithium hydroxide solution, and the temperature being kept at about 0-10xc2x0 C., preferably at about 5-8xc2x0 C. Normally, the reaction is finished after about one hour. There is thus obtained an aqueous suspension of the compound of formula (X).
Conveniently about one half of the above suspension of the compound of formula (X) thus obtained is then reacted with 1,4-diaminobenzene-2-sulfonic acid giving compound (XI) (the second half of this suspension being kept for subsequent reaction with compound (XI)). The 1,4-diaminobenzene-2-sulfonic acid is conveniently suspended in water at a temperature about 35-45xc2x0 C., preferably about 38-42xc2x0 C., whereupon caustic alkali is added, preferably an aqueous lithium hydroxide solution, until the pH reaches a value of about 8 and solution takes place. This solution is then added to the aforesaid suspension of the compound of formula (X) at a temperature of about 40-55xc2x0 C., preferably about 45-50xc2x0 C., and after this addition the pH, which has reached a value of about 5.5-6, is kept at this value by addition of caustic alkali, preferably aqueous lithium hydroxide solution. Normally, the reaction is finished after about 4-5 hours.
The second half of the aforesaid suspension of the compound of formula (X) is then given to the suspension obtained in the foregoing operation, conveniently at a temperature of about 40xc2x0 C., whereby the pH raises to about 6-7. The mixture is then heated, conveniently to a temperature of about 65-80xc2x0 C., preferably about 72-75xc2x0 C., which results in a decrease of the pH to about 5.5-6 at which value the pH is kept by addition of caustic alkali, preferably aqueous lithium hydroxide solution. In normal circumstances the reaction is finished after about 5-6 hours.
The suspension obtained in the foregoing operation is treated with 1-methylamino-ethyl-2-sulfonic acid which is conveniently utilized in the form of an aqueous solution of its sodium salt, or any other amine. This solution is added to the aforesaid suspension at a temperature of about 80-90xc2x0 C., preferably about 82-86xc2x0 C., whereby the pH rises from about 5 to about 10 and is then brought to and kept at about 8.2-8.6, preferably about 8.4, by addition of caustic alkali, preferably aqueous lithium hydroxide solution. The reaction is completed after 4-5 hours.
The resulting solution contains a mixture of compounds of formulae (I), (II) and (III), as defined hereinabove, in the form of alkali metal salts, preferably salts with lithium and sodium. This solution can be purified by conventional procedures, e.g. by filtration and/or ultrafiltration, and concentrated. If desired, the salts can be converted into the corresponding compounds of formulae (I), (II) and (III) or into other salts according to methods which are readily available to those skilled in the art. Conversely, compounds of formulae (I), (II) and (III) which may have been obtained by carrying out the synthesis described hereinabove in a slightly different manner, can be converted into salts. Suitable salts include the aforementioned lithium and sodium salts as well as potassium salts, ammonium salts etc. and inner salts.
The compounds according to the invention or their salts may be used for dyeing cationic dyeable materials such as: homo- or mixed-polymers of acrylonitrile, acid modified polyester or polyamide; wool; leather including low affinity vegetable-tanned leather; cotton; bast fibers such as hemp, flax, sisal, jute, coir and straw; regenerated cellulose fibers, glass or glass products comprising glass fibers; and substrates comprising cellulose for example paper and cotton. They may also be used for printing fibers, filaments and textiles comprising any of the above mentioned materials in accordance with known methods. Printing may be effected by impregnation of the material to be printed with a suitable printing paste comprising one or more compounds of the present invention. The type of printing paste employed, may vary depending on the material to be printed. Choice of a suitable commercially available printing paste or production of a suitable paste, is routine for one skilled in the art. Alternatively the compounds of the present invention may be used in the preparation of inks suitable for example for jet printing, in accordance with conventional methods.
Most preferably, the dyestuffs are used for dyeing or printing of paper e.g., sized or unsized, wood-free or wood-containing paper or paper-based products such as cardboard. They may be used in continuous dyeing in the stock, dyeing in the size press, in a conventional dipping or surface coloring process. The dyeing and printing of paper is effected by known methods.
The dyeings and prints and particularly those obtained on paper, show good fastness properties.
The compounds of formula (I) may be converted into dyeing preparations. Processing into stable liquid, preferably aqueous, or solid (granulated or powder form) dyeing preparations may take place in a generally known manner. Advantageously suitable liquid dyeing preparations may be made by dissolving the dyestuff or its salt in suitable solvents such as formamide, dimethylformamide, urea, glycols and ethers thereof, dextrin or addition products of boric acid with sorbitol which may be used together with water, optionally adding an assistant, e:g. a stabilizer. Such preparations may be obtained, for example, as described in French patent specification No. 1,572,030.
The compounds of formula (I) (in the corresponding salt form) have good solubility especially in cold water. Owing to their high substantivity the compounds of the present invention exhaust practically quantitatively and show a good build-up power. They can be added to the stock directly, i.e. without previously dissolving, as either a dry powder or granulate, without reducing the brilliance or the yield of color. They can also be used in soft water without loss of yield. They do not mottle when applied on paper, are not inclined to give two-sided dyeing on paper and are practically insensitive to filler or pH variations. They operate over a broad pH range, in the range of from pH 3 to 10. When producing sized or unsized paper, the waste water is essentially colorless. This feature, which is extremely important from an environmental view-point, when compared with similar known dyes, shows a marked improvement. A sized paper dyeing when compared with the corresponding unsized paper dyeing does not show any decrease in strength.
The paper dyeings or printings made with the compounds, in particular the metal-free forms, according to the invention are clear and brilliant and have very good light fastness: On exposure to light for a long time, the shade of the dyeing fades tone in tone. They show very good wet fastness properties; being fast to water, milk, fruit juice, sweetened mineral water, tonic water, soap and sodium chloride solution, urine etc. Furthermore, they have good alcohol fastness properties. The wet fastness properties are improved compared to known dyes showing otherwise similar properties. They do not exhibit a tendency towards two-sidedness.
Paper dyed or printed with the compounds of the present invention can be bleached oxidatively, a feature which is important for the recycling of waste and old paper/paper products. This property, together with the improved backwater results and wet-fastness, shows a marked improvement over known dyes having otherwise similar properties.
The compounds of the present invention may also be used to dye paper containing wood-pulp where even dyeings, having good fastness properties are obtained. Furthermore, they may be used for the production of coated paper in accordance with known methods. Preferably when coating, a suitable filler, for example kaolin, is employed in order to give a one-side coated paper.
The compounds of the present invention are also suitable for dyeing in combination with other dyes for example other cationic or anionic dyes. The compatibility of the compounds of the present invention when used as a dye in mixtures with other commercially available dyes, may be determined according to conventional methods. The thus obtained dyeings have good fastness properties.
The compounds of the present invention are also suitable for the preparation of ink jet inks.
The invention further provides a substrate which has been dyed or printed with a compound of the present invention. The substrate may be selected from any of the above mentioned substrates. A preferred substrate is a substrate comprising cellulose such as cotton or paper or a paper based product. The most preferred substrate is paper or a paper based product.